Process for producing paraffin-containing foam regulators

ABSTRACT

A process for producing pourable foam regulator granules containing a defoamer combination of a paraffin wax and a bisamide derived from diamines and carboxylic acids and an inorganic, water-soluble or water-dispersible carrier salt by pelletizing in a granulation mixer with intensive mixing 50 to 100 parts by weight of the inorganic carrier salt optionally with up to 5 parts by weight of an anionic or nonionic cellulose ether, adding 1 to 10 parts by weight of an aqueous alkali metal silicate or polymeric polycarboxylate solution and then adding 10 parts by weight of the defoamer combination heated to a temperature of 70° C. to 180° C.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a process for producing pourable foamregulator granules containing inorganic, water-soluble and/orwater-dispersible carrier salt and paraffin wax for use in laundry anddishwashing detergents by pelletizing and to the use of the granulesthus produced as foam-regulating constituents of laundry and dishwashingdetergents.

2. Discussion of Related Art

The use of bisamides as foam regulators for detergents is known fromDE-A 20 43 087. However, the formulations mentioned in that document donot have a uniform foam regulator effect over a wide temperature rangeand show weaknesses, particularly at low washing temperatures. Europeanpatent EP 087 233 describes a process for the production of alow-foaming detergent in which mixtures of an oily or wax-like substanceand bisamides are applied to a carrier powder, more particularly aspray-dried surfactant-containing detergent. The oily or wax-likesubstance may consist, for example, of vaseline with a melting point of20° C. to 120° C. In the Examples, mineral oil is used for this purpose.This component obviously serves primarily as a carrier or dispersant forthe bisamide. Although the use of 2% by weight of foam-regulatingmixture, based on the detergent, gives satisfactory results in theRoss-Miles Test, these quantities appear far too high for practicalpurposes. In addition, with this method of formulation, i.e. sprayingthe foam-regulating mixture onto the spray-dried surfactant-containingdetergent, the storage stability of the foam regulating componentpresent exclusively on the surface of the foam regulator is in danger ofbeing impaired by the production process, with the result that itsactivity decreases with increasing storage time. In order to increaseits effect and, at the same time, to reduce the necessary in-useconcentration, other known foam inhibitors, particularly polysiloxanesor polysiloxane/silica mixtures, are often added to these foamregulators. However, polysiloxanes, although well-known for theirfavorable foam-regulating effect, are relatively complicated to produce,which generally makes them more expensive as raw materials thancomparable active substances, and in addition have the disadvantage thattheir biological degradability in the wastewater is often not entirelysatisfactory. Other bisamide-containing formulations are known fromEuropean patents EP 075 437 and EP 094 250. However, the formulationsdescribed in these documents contain silicones. DE-A 28 57 155 describesdetergents with a foam regulator which contains hydrophobic silicondioxide and a mixture of solid and liquid hydrocarbons, optionally inadmixture with fatty acid esters. European patent application EP 309 931describes foam regulators based on a relatively expensive mixture ofparaffin wax and microcrystalline paraffin wax. International patentapplication WO 93/17772 describes paraffin-based foam regulatorscontaining carboxylic acid bisamide of which the paraffin wax componenthas as small a liquid content as possible and, preferably, contains noliquid at all. According to the document in question, preferred paraffinwax mixtures have a liquid content at 30° C. of less than 10% by weightand a liquid content at 40° C. of less than 30% by weight. In somecases, however, foam regulators of the type in question performunsatisfactorily in low-temperature machine washing which, recently, hasacquired increasing significance.

European patent application EP 0 008 829 describes solid detergentswhich contain a foam control system of wax, hydrophobicized silica gel,certain nonionic dispersants and, optionally, silicones which is presentin the form of an intimate mixture with the other ingredients of thedetergent. According to the document in question, the preliquefied foamcontrol system may be sprayed onto preformed, more particularlyspray-dried, carrier granules which contain all or part of the otherdetergent ingredients. The several stages involved in this productionprocess make it relatively complicated.

DE-A 34 36 194 describes a process for the production of pourable foamregulator granules by spray drying of an aqueous dispersion containingwater-insoluble foam inhibitor, inorganic carrier salt and certaincellulose ether mixtures. Because of the high temperatures prevailingunder the spray-drying conditions, a process such as this can lead toproducts which do not always show optimal foam-regulating performance,particularly where low-melting paraffin waxes are used.

However, the use of such low-melting paraffins is of particular interestby virtue of their considerable effectiveness in the low-temperaturewash programs being increasingly used by the consumer.

Additionally, there was a need to develop a process for the productionof stable foam regulator formulations which, in the production ofparticulate laundry and dishwashing detergents, would withstand mixingwith the other ingredients with their granular structure intact andwithout any dust emission and which, nevertheless, would dissolvequickly and completely and release the foam-inhibiting agent underin-use conditions.

DESCRIPTION OF THE INVENTION

The process according to the invention for producing pourable foamregulator granules containing a defoamer combination of a paraffin waxand a bisamide derived from diamines and carboxylic acids and inorganic,water-soluble and/or water-dispersible carrier salt is characterized inthat a pelletizing step is carried out in a granulation mixer byintensively mixing a quantity of 50 to 100 parts by weight and, moreparticularly, 60 to 85 parts by weight of the inorganic carrier salt,preferably containing alkali metal sulfate and/or alkali metalcarbonate, optionally with a quantity of up to 5 parts by weight and,more particularly, 1 to 3 parts by weight of an anionic and/or nonioniccellulose ether, adding a quantity of 1 to 10 parts by weight and, moreparticularly, 2 to 8 parts by weight of an aqueous alkali metal silicateand/or polymeric polycarboxylate solution while granulation continuesand then adding 10 parts by weight of the defoamer combination heated toa temperature of 70° C. to 180° C. In a preferred embodiment, 5 to 20parts by weight and, more particularly, 7 to 15 parts by weight of wateror an aqueous sodium silicate and/or polymeric polycarboxylate solutionare added after the defoamer combination. In these cases, the granulesobtained have a particularly stable structure. It is remarkable that,where this procedure is adopted, the carrier material does not have toheated and, instead, can be left at ambient temperature or at thetemperature generated by the energy introduced through the mixingprocess.

In another preferred embodiment of the process according to theinvention, the preferably phosphate-free carrier salt mixture ishomogenized, optionally after addition of the cellulose ether mixture,for 5 seconds to 30 seconds, more particularly in an intensive mixer,for example an FS30 Fukae® an Eirich® mixer, a Lödige® plowshare mixeror a Shugi® mixer, the aqueous alkali metal silicate solution is addedas quickly as possible, the liquid molten defoamer combination is thenintroduced, after which the water or the aqueous alkali metal silicateand/or polycarboxylate solution, if any, is added over a period of 10seconds to 30 seconds and the granulation process is continued for 10seconds to 10 minutes. The ingredients used in liquid form can beintroduced through the spray nozzles normally present in granulationmixers.

The defoamer combination preferably consists of 70% by weight to 95% byweight of paraffin wax or paraffin wax mixture and of 5% by weight to30% by weight of a bisamide derived from C₂₋₇ diamines and saturatedC₁₂₋₂₂ carboxylic acids. The paraffin wax is solid at room temperature,at least 35% by weight and, more particularly, at least 45% by weightand less than 100% by weight preferably being present in liquid form ata temperature of 40° C.

The paraffin wax present in the defoamer combination is generally acomplex mixture with no clear-cut melting point. It is normallycharacterized by determining its melting range by differentialthermoanalysis (DTA), as described in “The Analyst” 87 (1962), 420,and/or its solidification point. This is understood to be thetemperature at which the wax changes from the liquid to the solid stateby gradual cooling. Paraffins containing less than 17 carbon atomscannot be used for the purposes of the invention so that theirpercentage content in the paraffin wax mixture should be as small aspossible and, preferably, is below the limit significantly measurable bystandard analytical techniques, for example gas chromatography. Waxeswhich solidify at 20° C. to 70° C. are preferably used. It is importantin this regard to bear in mind the fact that even paraffin wax mixtureswhich appear solid at room temperature can contain varying proportionsof liquid paraffin. In the paraffin waxes suitable for use in accordancewith the invention, the liquid component at 40° C. is as large aspossible without ever reaching 100% at that temperature. Preferredparaffin wax mixtures have a liquid component at 40° C. of at least 50%by weight and, more particularly, between 55% by weight and 80% byweight and a liquid component at 60° C. of at least 90% by weight. Theresult of this is that the paraffins are free-flowing and pumpable attemperatures down to at least 70° C. and preferably down to at least 60°C. In addition, it is important to bear in mind that the paraffinsshould not contain any volatile components. Preferred paraffin waxescontain less than 1% by weight and, more particularly, less than 0.5% byweight of components capable of evaporating at 110° C./normal pressure.Paraffin waxes suitable for use in accordance with the invention can beobtained, for example, under the trade names of Lunaflex® from theFuller company and Deawax® from DEA Mineralöl AG.

The second component of the defoamer combination consists of bisamidesderived from saturated C₁₂₋₂₂ and, more particularly C₁₄₋₁₈ fatty acidsand C₂₋₇ alkylene diamines. Suitable fatty acids include, for example,lauric acid, myristic acid, stearic acid, arachic acid and behenic acidand the mixtures thereof obtainable from natural fats or hydrogenatedoils, such as tallow or hydrogenated palm oil. Suitable diamines are,for example, ethylenediamine, 1,3-propylenediamine,tetramethylenediamine, pentamethylenediamine, hexamethylenediamine,p-phenylenediamine and toluylenediamine. Preferred diamines areethylenediamine and hexamethylenediamine. Particularly preferredbisamides are bis-myristoyl ethylenediamine, bis-palmitoylethylenediamine, bis-stearoyl ethylenediamine and mixtures thereof andthe corresponding derivatives of hexamethylenediamine.

As described in European patent application EP 0 309 931, the bisamidesare preferably present in fine-particle form and, in particular, have amean particle size of less than 50 μm. The maximum size of the particlesis preferably below 20 μm, at least 50% and, more particularly, at least75% of the particles being smaller than 10 μm.

The defoamer combination may be produced by introducing thefine-particle bisamide into a melt of the paraffin wax and homogenizingit therein by intensive mixing. To this end, the melt should have atemperature of at least 90° C. and at most 200° C. The temperature atwhich the paraffin wax is kept in order to apply it to the carriermaterial is preferably in the range from 100° C. to 150° C. The presenceof a stable dispersion of the bisamide particles in the paraffin matrix,which is crucial to the effectiveness of the foam regulator, can beachieved through a particle size corresponding to the above definition.In order to achieve this dispersion state, a bisamide having theappropriate particle size from the outset may be used and dispersed or acoarser starting material may be used and the melt subjected tointensive stirring or grinding in colloid mills, toothed disc mills orball mills until the required particle size has been reached. Completemelting of the bisamides in the paraffin melt and subsequent cooling totemperatures below their solidification point by application to thecolder carrier material can also lead to a correspondingly fine particlesize distribution of the bisamides.

The preferably phosphate-free carrier salt mixture for the defoamercombination contains readily water-soluble inorganic salts such as, forexample, alkali metal sulfates, alkali metal carbonates and/or alkalimetal silicates. In one preferred embodiment of the invention, itcontains both alkali metal carbonate and alkali metal sulfate, thealkali metal sulfate in particular being responsible for the gooddissolving properties of the granules according to the invention. Thecarrier material may additionally contain other water-soluble orwater-insoluble, water-dispersible substances. Suitable additionalcarrier materials include in particular alkali metal chlorides, alkalineearth metal silicates, alumosilicates, for example zeolite A, P and Xand layer silicates, for example bentonite. The carrier salt mixturepreferably contains no more than 20% by weight and, more particularly,from 1% by weight to 15% by weight, based on the final granules, of theadditional carrier materials.

Cellulose ethers suitable for use in accordance with the inventioninclude, in particular, alkali metal carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyethyl cellulose and so-calledcellulose mixed ethers such as, for example, methyl hydroxyethylcellulose and methyl hydroxypropyl cellulose and mixtures thereof.Mixtures of sodium carboxymethyl cellulose and methyl cellulose in whichthe carboxymethyl cellulose normally has a degree of substitution of 0.5to 0.8 carboxymethyl groups per anhydroglucose unit and the methylcellulose a degree of substitution of 1.2 to 2 methyl groups peranhydroglucose unit are preferably used. Cellulose ethers such as theseare normally used in solid form in the process according to theinvention, although they may also be used in the form of aqueoussolutions which may be preswollen in the usual way. Cellulose ethermixtures preferably contain alkali metal carboxymethyl cellulose andnonionic cellulose ether in ratios by weight of 80:20 to 40:60 and, moreparticularly, 75:25 to 50:50.

The alkali metal silicate usable in the carrier material both in solidform and in the form of the aqueous solution mentioned is preferably asodium sililicate with a molar Na₂O to SiO₂ ratio of 1:2 to 1:3.35. Theuse of such silicates results in particularly favorable granuleproperties, more particularly high abrasion resistance and a highdissolving rate in water. The aqueous alkali metal silicate solution, ifused, preferably contains 25% by weight to 60% by weight and, moreparticularly, 30% by weight to 40% by weight of alkali metal silicate.

The polymeric polycarboxylates optionally used include in particular thepolycarboxylates of International patent application WO 93/16110obtainable by oxidation of polysaccharides and polymeric acrylic acids,methacrylic acids, maleic acids and copolymers thereof which may alsocontain small amounts of polymerizable substances with no carboxylicacid functionality in copolymerized form. The relative molecular weightof the homopolymers of unsaturated carboxylic acids is generally in therange from 5,000 to 200,000 and that of the copolymers in the range from2,000 to 200,000 and preferably in the range from 50,000 to 120,000,based on free acid. A particularly preferred acrylic acid/maleic acidcopolymer has a relative molecular weight of 50,000 to 100,000. Suitablebut less preferred compounds of this class are copolymers of acrylicacid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers,vinyl ester, ethylene, propylene and styrene, in which the acid makes upat least 50% by weight. Terpolymers containing two unsaturated acidsand/or salts thereof as monomers and vinyl alcohol and/or a vinylalcohol derivative or a carbohydrate as the third monomer may also beused. The first acidic monomer or its salt is derived from amonoethylenically unsaturated C₃₋₈ carboxylic acid and preferably from aC₃₋₄ monocarboxylic acid, particularly (meth)acrylic acid. The secondacidic monomer or its salt may be a derivative of a C₄₋₈ dicarboxylicacid, maleic acid being particularly preferred. In this case, the thirdmonomeric unit is formed by vinyl alcohol and/or preferably anesterified vinyl alcohol. Vinyl alcohol derivatives in the form of anester of short-chain carboxylic acids, for example C₁₋₄ carboxylicacids, with vinyl alcohol are particularly preferred. Preferred polymerscontain 60% by weight to 95% by weight and, more particularly, 70% byweight to 90% by weight of (meth)acrylic acid or (meth)acrylate,preferably acrylic acid or acrylate, and maleic acid or maleate and 5%by weight to 40% by weight and preferably 10% by weight to 30% by weightof vinyl alcohol and/or vinyl acetate. Polymers in which the ratio byweight of (meth)acrylic acid or (meth)acrylate to maleic acid or maleateis between 1:1 and 4:1, preferably between 2:1 and 3:1 and moreparticularly between 2:1 and 2.5:1 are most particularly preferred (boththe quantities shown and the ratios by weight apply to the acids). Thesecond acidic monomer or its salt may even be a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl group,preferably a C₁₋₄ alkyl group, or an aromatic radical preferably derivedfrom benzene or benzene derivatives. Preferred terpolymers contain 40%by weight to 60% by weight and, more particularly, 45% by weight to 55%by weight of (meth)acrylic acid or (meth)acrylate, preferably acrylicacid or acrylate, 10% by weight to 30% by weight and preferably 15% byweight to 25% by weight of methallyl sulfonic acid or methallylsulfonate and, as the third monomer, 15% by weight to 40% by weight andpreferably 20% by weight to 40% by weight of a carbohydrate. Thiscarbohydrate may be, for example, a monosaccharide, disaccharide,oligosaccharide or polysaccharide, mono-, di- or oligosaccharides beingpreferred. Sucrose is particularly preferred. The use of the thirdmonomer presumably introduces predetermined weak spots into the polymerwhich are responsible for its ready biodegradability. These terpolymersmay be produced in particular by the processes described in Germanpatent DE 42 21 381 and in German patent application DE 43 00 772 andgenerally have a relative molecular weight of 1,000 to 200,000,preferably in the range from 200 to 50,000 and more preferably in therange from 3,000 to 10,000. Other preferred copolymers are thecopolymers described in German patent applications DE 43 03 320 and DE44 17 734 which preferably contain acrolein and acrylic acid/acrylicacid salts or vinyl acetate as monomers. The polymeric polycarboxylatesare preferably used in the form of 30 to 50% by weight aqueoussolutions. All the acids mentioned are generally used in the form oftheir water-soluble salts, more particularly their alkali metal salts.

The foam regulator granules obtainable by the process according to theinvention, which are suitable for use in laundry or dishwashingdetergents, preferably contain 60% by weight to 90% by weight ofinorganic carrier salt or carrier salt mixture, 0.5% by weight to 5% byweight of a mixture of alkali metal carboxymethyl cellulose and nonioniccellulose ether, more particularly in a ratio by weight of 80:20 to40:60, 5% by weight to 30% by weight and, more particularly, 8% byweight to 20% by weight of defoamer combination, 0.5% by weight to 10%by weight and, more particularly, 1% by weight to 5% by weight of alkalimetal silicate, 0.5% by weight to 10% by weight and, more particularly,1% by weight to 5% by weight of polymeric polycarboxylate and up to 15%by weight and, more particularly, 2% by weight to 10% by weight ofwater. A water content in the above-mentioned range is normallyestablished automatically if the process parameters according to theinvention are observed. If their water content is too high, however,foam regulator granules produced in accordance with the invention mayalso be dried by conventional methods, for example in fluidized beddryers, after the pelletizing steps.

Foam regulators produced in accordance with the invention are preferablyfree from surfactants with an emulsifying or dispersing effect.Surfactants are understood to be surface-active compounds of which partof the molecule is hydrophobic and which contain hydrophilic anionic,ampholytic, zwitterionic, cationic and nonionic groups. They develop acleaning or emulsifying effect in the form of an aqueous solution ordispersion. The hydrophobic part of the molecule generally consists of ahydrocarbon radical or a substituted hydrocarbon radical or asubstantially water-insoluble polyglycol ether group, for example apolypropylene glycol or polybutylene glycol ether group. Compounds witha non-polar molecular structure, more particularly the above-mentionedcellulose ethers or polymeric polycarboxylates, which can also develop adispersing effect in water under certain conditions, do not come underthe definition of “surfactants” and may be present.

The foam regulator granules according to the invention normally havebulk densities of 600 grams per liter to 1400 grams per liter and, moreparticularly, 800 grams per liter to 1200 grams per liter. In general,more than 80% by weight, preferably more than 90% by weight and, inparticular, more than 95% by weight of the granules have particle sizesof 0.1 mm to 2.0 mm. In one preferred embodiment, the average particlesize of the foam inhibitor granules is in the range from 0.4 mm to 0.8mm. In a particularly preferred embodiment, only very small percentagesof the granules have particle sizes outside this range.

The foam regulator granules obtainable by the process according to theinvention are stable in storage, can readily be mixed with typicalpowder-form ingredients of laundry and dishwashing detergents withoutany dust emission and are completely flushed into washing machines withno residues. Accordingly, the present invention also relates to theiruse as foam-regulating components of laundry and dishwashing detergents.They dissolve quickly at temperatures below 60° C. and, accordingly,release the foam-inhibiting agent even under low-temperature washingconditions or even in the initial phase of high-temperature washing,their foam-regulating performance remaining at a consistently high levelthroughout the wash cycle.

The foam regulator granules according to the invention are alsodistinguished in particular by the fact that, in contrast to spray-driedformulations, the active foam-regulating agent develops a high level ofactivity in the final particles. The granules according to the inventionhave a foam-regulating performance which spray-dried products of similarcomposition only achieve with larger contents of active substance.

EXAMPLES Example 1

In a 135 liter Lödige® plowshare mixer, 16.2 kg of sodium sulfate and0.5 kg of a mixture of sodium carboxymethyl cellulose and methylcellulose (ratio by weight about 70:30) containing 66% by weight ofactive substance (rest sodium chloride and sodium glycolate) werehomogenized for 15 seconds with the chopping unit switched on. 0.5 kg ofa 34% by weight aqueous sodium silicate solution and then 0.7 kg of anaqueous 34% by weight solution of polymeric polycarboxylate wereintroduced over a period of 15 seconds. 2 kg of a melt heated to 150° C.of 88% by weight of paraffin (solidification point according to DIN ISO2207 45° C., liquid content ca. 66% by weight at 40° C. and ca. 96% at60° C.) and 12% by weight of ethylenediamine bis-stearoyl amide werethen sprayed in over a period of 180 seconds. 1.6 kg of water was thenadded over a period of 30 seconds, followed by mixing for 120 seconds.The moist granules were then dried at 80° C. in a fluidized-bed dryer.Hard, dry free-flowing foam regulator granules G1 with a bulk density of1200 grams per liter were obtained, 98% by weight consisting ofparticles larger than 0.1 mm in size and 60% by weight consisting ofparticles between 0.8 mm and 2.0 mm in size.

Example 2

Detergents were produced simply by mixing quantities of 1.5% by weightof foam regulator granules B1 and C1 with a standard heavy-dutydetergent powder containing 21% by weight of zeolite NaA, 20% by weightof sodium sulfate, 3% by weight of sodium silicate, 10% by weight ofsodium carbonate, 3.5% by weight of polymeric polycarboxylate (Sokalan®CP5), 8% by weight of sodium alkyl benzene sulfonate, 2% by weight ofnonionic surfactant, 1.5% by weight of soap, 22% by weight of sodiumperborate and 2% by weight of TAED, balance to 100% by weight water. Itwas shown by washing tests (Miele® W918 drum-type washing machine, 3.5kg clean washing, water hardness 3°d, dosage 130 g detergent) that thefoam regulators according to the invention are more effective,particularly at low temperatures, than a known foam regulator tested forcomparison (C1) which contained the same ingredients as B1, but whichhad been produced by spray drying and which therefore had to contain amore heat-resistant and higher-melting paraffin (liquid content ca. 9%by weight at 40° C., ca. 66% at 60° C.). The foam scores shown in Table2 below were obtained (scale of 0 to 6:0=no foam; 3=bull's eye ofwashing machine half-filled with foam; 5=bull's eye of washing machinecompletely filled with foam; 6=loss of liquor through overfoaming; thevalues were read off after the specified washing time for the 40° C.program and in the specified temperature range for the 90° C. program).After storage (8 weeks in laminated boxes at 30° C./80% relative airhumidity) of the detergent containing the foam regulator granules B1according to the invention, there was no sign of any deterioration inthe foam-regulating performance.

TABLE 2 Foam scores of the foam regulators in the detergent Foam regu-40° C. 90° C. lator <20 mins. <40 mins. >40 mins. <55° C. <75° C. >75°C. B1 0-1 0-2 0-2 0-1 0-2.5 2.0-3.5 C1 >4 >4 >4 >4 >4 >4

What is claimed is:
 1. The process of producing pourable foam regulatorgranules containing a defoamer combination of a paraffin wax and abisamide derived from diamines and carboxylic acids and inorganic,water-soluble or water-dispersible carrier salt, comprising pelletizingin a granulation mixer by intensively mixing 50 to 100 parts by weightof said inorganic carrier salt, optionally with up to 5 parts by weightof an anionic or nonionic cellulose ether, adding 1 to 10 parts byweight of an aqueous alkali metal silicate or polymeric polycarboxylatesolution, and then adding 10 parts by weight of said defoamercombination heated to a temperature of 70° C. to 180° C.
 2. A process asin claim 1 including adding 5 to 20 parts by weight of water, or anaqueous sodium silicate solution or a polymeric polycarboxylate solutionto said granules after adding said defoamer combination.
 3. A process asin claim 1 wherein 60 to 85 parts by weight of said inorganic carriersalt, 1 to 3 parts by weight of cellulose ether and 2 to 8 parts byweight of said aqueous alkali metal silicate or organic polycarboxylatesolution are used.
 4. A process as in claim 2 wherein said carrier saltis homogenized, optionally after addition of said cellulose ether, for 5seconds to 30 seconds, adding said water, said aqueous alkali metalsilicate solution or polycarboxylate solution, adding said defoamercombination in molten form over a period of 10 seconds to 30 seconds,and granulating the mixture for 10 seconds to 10 minutes.
 5. A processas in claim 1 wherein said defoamer composition consists of 70% to 95%by weight of paraffin wax and 5% to 30% by weight of a bisamide derivedfrom C₂-C₇ diamines and saturated C₁₂-C₂₂ carboxylic acids.
 6. A processas in claim 5 wherein said paraffin wax is a solid at room temperature,and at least 50% by weight, and less than 100% by weight thereof ispresent in liquid form at a temperature of 40° C.
 7. A process as inclaim 1 wherein said polymeric polycarboxylate is selected from thegroup consisting of polycarboxylates obtained by oxidation ofpolysaccharides and polymeric acrylic acids, methacrylic acids, maleicacids and copolymers thereof which may also contain small quantities ofpolymerizable substances having no carboxylic acid functionality incopolymerized form.
 8. A process as in claim 1, wherein said polymericpolycarboxylate is selected from the group consisting of terpolymers andquaterpolymers which contain two unsaturated acids and salts thereof asmonomers and vinyl alcohol or a vinyl alcohol derivative or acarbohydrate as the third or fourth monomer.
 9. A process in claim 1wherein said cellulose ether is selected from the group consisting ofalkali metal carboxymethyl cellulose, methyl cellulose, ethyl cellulose,hydroxyethyl cellulose and cellulose mixed ethers such as methylhydroxyethyl cellulose and methyl hydroxypropylcellulose, and mixturesthereof.
 10. Foam regulator granules produced by the process of claim 1containing 60% to 90% by weight of inorganic carrier salt or carriersalt mixture, 0.5% to 5% by weight of a mixture of alkali metalcarboxymethyl cellulose and nonionic cellulose ether in a ratio byweight of 80:20 to 40:60, 5% to 30% by weight of the defoamercombination, 0.5% to 10% by weight of alkali metal silicate, 0.5% to 10%by weight of polymeric polycarboxylate, and up to 15% by weight ofwater.
 11. Foam regulator granules as in claim 10 having a bulk densityof 600 grams per liter to 1400 grams per liter.
 12. Foam regulatorgranules as in claim 10 wherein more than 80% by weight of the granuleshave a particle size of 0.1 mm to 2.0 mm.
 13. Foam regulator granules asin claim 12 having a mean particle size in the range from 0.4 mm to 0.8mm.
 14. The process of controlling foam generated from a laundry ordishwashing detergent solution comprising adding to said solutionpourable foam regulator granules containing a defoamer combination of aparaffin wax and a bisamide derived from diamines and carboxylic acidsand inorganic, water-soluble or water-dispersible carrier salt, saidgranules having been obtained by pelletizing in a granulation mixer byintensively mixing 50 to 100 parts by weight of said inorganic carriersalt, optionally with up to 5 parts by weight of an anionic or nonioniccellulose ether, adding 1 to 10 parts by weight of an aqueous alkalimetal silicate or polymeric polycarboxylate solution, and then adding 10parts by weight of said defoamer combination heated to a temperature of70° C. to 180° C.
 15. A process as in claim 14 wherein to said granulesis added 5 to 20 parts by weight of water, or an aqueous sodium silicatesolution or a polymeric polycarboxylate solution after adding saiddefoamer combination.
 16. A process as in claim 14 wherein said granulescontain 60 to 85 parts by weight of said inorganic carrier salt, 1 to 3parts by weight of cellulose ether and 2 to 8 parts by weight of saidaqueous alkali metal silicate or organic polycarboxylate solution.
 17. Aprocess as in claim 14 wherein said granules have been prepared byhomogenizing said carrier salt, optionally after addition of saidcellulose ether, for 5 seconds to 30 seconds, adding said water, saidaqueous alkali metal silicate solution or polycarboxylate solution,adding said defoamer combination in molten form over a period of 10seconds to 30 seconds, and granulating the mixture for 10 seconds to 10minutes.
 18. A process as in claim 14 wherein said defoamer compositionconsists of 70% to 95% by weight of paraffin wax and 5% to 30% by weightof a bisamide derived from C₂-C₇ diamines and saturated C₁₂-C₂₂carboxylic acids.
 19. A process as in claim 18 wherein said paraffin waxis a solid at room temperature, and at least 35% by weight and less than100% by weight thereof is present in liquid form at a temperature of 40°C.
 20. A process as in claim 14 wherein said polymeric polycarboxylateis selected from the group consisting of polycarboxylates obtained byoxidation of polysaccharides and polymeric acrylic acids, methacrylicacids, maleic acids and copolymers thereof which may also contain smallquantities of polymerizable substances having no carboxylic acidfunctionality in copolymerized form.